The findings of per- and polyfluoroalkyl substances (PFAS) in humans and the environment all over the world have raised concerns and public awareness for this group of man-made chemicals. In the last three decades, this led to different regulatory restrictions for specific PFAS as well as shifts in the production and usage of these substances. In this study, we analyzed the PFAS levels of 100 human blood plasma samples collected from 2009 to 2019 for the German Environmental Specimen Bank (ESB) to further elucidate the time course of exposure towards this substance group as shown by Schröter-Kermani et al., (2013) with samples from 1982 to 2010. A spectrum of 37 PFAS, including perfluorocarboxylic (PFCA) and –sulfonic acids (PFSA) as well as potential precursors and substitutes like ADONA, GenX or F-53B was analyzed by UHPLC coupled with high-resolution mass spectrometry. Validation was successful for 33 of the substances.

The two legacy substances perfluorooctanoic acid (PFOA) and perfluorooctane sulfonic acid (PFOS) were detected in every sample of the 2009–2019 dataset and showed the highest concentrations with ranges of 0.27–14.0 ng/mL and 1.21–14.1 ng/mL, respectively. A significant portion of total PFOS analytes was present as branched isomers (mean: 34 ± 7%). High detection frequencies of 95% and 82% were also found for perfluorohexane sulfonic acid (PFHxS) and perfluorononanoic acid (PFNA), respectively, but in lower concentrations (PFHxS: <LOQ – 4.62 ng/mL; PFNA: <LOQ – 3.66 ng/mL) than PFOA and PFOS. Besides other PFCA and PFSA only 8:2 fluorotelomer sulfonic acid (8:2 FtS) and N-methyl perfluorooctane sulfonamidoacetic acid were detected in very few samples. In combination with the previous results from 1982 to 2010, declining temporal trends were observed for all PFAS (PFOA, PFNA, PFHxS, and PFOS) frequently detected in the ESB samples. The results of this study indicate a decrease in human exposure to known PFAS in Germany over the last three decades and emphasize the importance of long-term human biomonitoring studies for investigating the effects of chemical regulation.

全世界人类和环境中的全氟和多氟烷基物质（PFAS）的发现引起了人们对这一类人造化学物质的关注和公众意识。在过去的三十年中，这导致对特定PFAS的不同监管限制以及这些物质的生产和使用发生了变化。在这项研究中，我们分析了2009年至2019年德国环境标本银行（ESB）收集的100份人类血浆样品的PFAS水平，以进一步阐明暴露于该物质组的时间过程，如Schröter-Kermani等人所示。 （2013年），样本从1982年到2010年。共有37种PFAS，包括全氟羧酸（PFCA）和–磺酸（PFSA）以及潜在的前体和替代物，例如ADONA，通过UHPLC和高分辨率质谱分析GenX或F-53B。33种物质的验证成功。

在2009-2019年数据集中的每个样本中都检测到两种传统物质全氟辛酸（PFOA）和全氟辛烷磺酸（PFOS），其最高浓度分别为0.27-14.0 ng / mL和1.21-14.1 ng / mL。 。PFOS分析物的很大一部分以支链异构体形式存在（平均值：34±7％）。全氟己烷磺酸（PFHxS）和全氟壬酸（PFNA）的检出率分别为95％和82％，但浓度较低时（PFHxS：<LOQ – 4.62 ng / mL； PFNA：<LOQ – 3.66 ng / mL）。除其他PFCA和PFSA外，仅8：2氟调聚物磺酸（8：2 FtS）和N在极少数样品中检测到-甲基全氟辛烷磺酰胺基乙酸。结合1982年至2010年的先前结果，观察到ESB样本中经常检测到的所有PFAS（PFOA，PFNA，PFHxS和PFOS）的时间趋势都在下降。这项研究的结果表明，过去三十年来，德国人接触已知PFAS的人数有所减少，并强调了长期的人类生物监测研究对于研究化学调控作用的重要性。